Filter dyes for rapid processing applications

ABSTRACT

The synthesis and the application of new dyes is described, said new dyes being incorporated in non-migratory state in hydrophilic colloid layers of photographic materials wherefrom they can be rapidly removed after being quickly decolorized in alkaline aqueous liquids used in the processing of said materials. The filter dyes have an amide function or a derivative therefrom as a substituent at the mono- or trimethine chain.

DESCRIPTION Field of the invention

The present invention relates to filter dyes and their use asantihalation and anti-cross-over dyes in photographic elements.

Background of the Invention

Non-spectrally sensitizing dyes are widely used in photographicelements, particularly in photographic elements of the silver halidetype. They may be used in a photosensitive silver halide emulsion layeras screening dyes, in an undercoat adjacent to the photosensitive layerand/or in a backing layer on the side of the support opposite to thephotosensitive layer(s) to absorb reflected and scattered light therebyserving as antihalation dye or in an overcoat or interlayer to shield aparticular photosensitive layer against undesired exposure beingtherefore referred to as filter or absorber dye, thereby adjusting thesensitivity of a photographic element as required in the productionspecifications.

For example in order to improve image sharpness an absorber dye can bepresent in one or more filter layers between silver halide emulsionlayers that are coated at opposite sides of a transparent film supportof an X-ray recording material. The imagewise exposure of said recordingmaterial proceeds in a cassette between a pair of X-ray intensifyingscreens that each are held in contact with an adjacent silver halideemulsion layer. By said arrangement the imaging light that would crossthe support and to some extent becomes scattered thereby, isconsiderably attenuated and cannot give rise to an unsharp image in anopposite silver halide emulsion layer.

Spectrally the dye absorption spectrum should approximately be equal tothe sensitivity spectrum of the corresponding silver halide emulsion inthe layer of which a sharp image has to be reproduced.

On the one hand it is very important that filter dyes remain, i.e. thatthey are non-migratory, in the layer wherein they have been incorporatedespecially when this layer is in direct contact with the silver halideemulsion layer in order to prevent a desensitizing action on the silverhalide. On the other hand the filter dyes may not stain the photographicmaterial after image processing. Therefore preference is given to filterdyes that decolorize or can be removed from the photographic element inthe processing stage. This requirement is nowadays becoming more andmore stringent as rapid processing times are of increasing interest.

As described in U.S. Pat. No. 3,560,214 dyes comprising a carboxyl andphenyl substituted pyrazoline nucleus linked through a methine group toa dialkylaminophenyl group can be removed relatively easily in alkalineaqueous processing liquids but lack sufficient fastness to diffusion inhydrophilic colloid layers.

Other filter dyes characterized by the presence of a 2-pyrazolin-5-onenucleus substituted with a carboxyphenyl group and including a methinegroup or chain linked to a dialkylamino group are described in U.S. Pat.No. 4,857,446. The decolorization of said filter dyes proceeds veryrapidly in alkaline aqueous processing baths. The monomethine dyes havean absorption spectrum of which the maximum is in the shorter wavelengthrange of the visible spectrum so that normally a second filter dye isneeded to block or absorb green light and even a third one to absorbradiations of longer wavelengths, e.g. radiations in the red or even inthe infrared region.

Once a filter dye has been selected, the problem is how to get thefilter dye in a coated layer so that all the requirements mentionedpreviously are met.

One of the possibilities is to make use of solid particle dispersions ofwater insoluble dyes as has been described in EP 0,384,633 A2; EP0,323,729 A2; EP 0,274,723 B1, EP 0,276,566 B1, EP 0,351,593 A2 and U.S.Pat. Nos. 4,900,653; 4,904,565; 4,949,654; 4,940,654; 4,948,717;4,988,611 and 4,803,150.

Another possibility is offered in Research Disclosure 19551 (Jul. 1980)which describes an approach of associating hydrofobic compounds withlatex polymer particles.

EP 0,401,709 A2 describes the dissolution of hydrophobic dyes into oildroplets being substantially insoluble in water and the preparation ofthe corresponding oilformer dispersions or loaded polymer latexdispersions.

To prevent dye wandering, the dye is often coated with a mordant to bindthe dye in the layer in which it is coated as is e.g. illustrated inU.S. Pat. No. 2,527,583. As dye mordants polymers are often used.

Another possibility is offered by adsorption of dyes at the surface ofvery fine light-insensitive silver halide crystals with the expectabledisadvantages of the coating of more silver halide crystals and possiblyfixation difficulties.

Very few dyes satisfy the above requirements especially when rapidprocessing is concerned. Moreover, apart from the requirement ofnon-diffusibility and of rapid decolorizing or removal by rapidprocessing that the dyes should meet, they should have high stability inthe photographic material, not only under the influence of theingredients present in the emulsion layers prior to coating, butespecially under severe storage conditions of the packed material e.g.under circumstances of high temperatures and high degrees of humidity.

OBJECTS AND SUMMARY OF THE INVENTION

It is an object of the present invention to provide new dyes that can beincorporated in non-migratory state in hydrophilic colloid layers ofphotographic materials wherefrom they can be rapidly removed in alkalineaqueous liquids used in the processing of said materials.

It is a further object of the invention to provide new dyes providinghigh density in the required spectral region, thereby reducing thecross-over effect in double-sided photographic elements, particularlyradiographic materials.

Other objects will become apparent from the description hereinafter.

In accordance with the present invention dyes are provided correspondingto the following general formula (I): ##STR1## wherein n represents 0 or1;

represents 0, 1 or 2;

Q represents the atoms necessary to form an acidic nucleus such aspyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoine,oxazolidindione, thio-oxazolidindione, isoxazolinone etc.;

R₁ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl, COOR₂,NHCOR₃ or NHSO₂ R₄ with R₂ representinghydrogen or substituted or unsubstituted alkyl, R₃ and R₄ representingsubstituted or unsubstituted alkyl, or substituted or unsubstitutedaryl;

X represents OR₅, SR₅ or NR₆ R₇ wherein R₅ represents H, substituted orunsubstituted alkyl, substituted or unsubstituted aryl and

each of R₆ and R₇ which may be the same or different representshydrogen, substituted or unsubstituted alkyl, substituted orunsubstituted aryl or the necessary atoms, e.g. trimethylene, to form aring together with the N-atom to which they are attached and the C-atomof the phenylene ring in ortho position with respect to said N-atom; R₆and R₇ together may also represent the necessary atoms to form a ringwith the N-atom to which they are attached; L₁, L₂, L₃ representsubstituted or unsubstituted methine with the proviso that at least oneof L₁, L₂ or L₃ must be substituted by --CONR₈ R₉ ;

R₈ and R₉ which may be the same or different represent hydrogen,substituted or unsubstituted alkyl, substituted or unsubstituted aryl,NH₂, NHR₁₀, NR₁₁ R₁₂ with R₁₀, R₁₁ and R₁₂ representing a substituted orunsubstituted alkyl, or a substituted or unsubstituted aryl and whereinat least one of R₁ to R₁₂ contains an ionizable group.

More preferably dyes of the present invention correspond to formula(II): ##STR2## wherein each of n, p, X, R₁, L₁, L₂ and L₃ has one of themeanings given hereinbefore and wherein

R₁₃ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl, or sulfolanyl,

R₁₄ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted aryl, COOR₂, NHCOR₃, NHSO₂ R₄, with R₂, R₃ and R₄representing hydrogen, substituted or unsubstituted alkyl, R₃ and R₄representing hydrogen, substituted or unsubstituted alkyl, orsubstituted or unsubstituted aryl, and wherein at least one of R₁ to R₁₄contains an alkali-soluble group.

In accordance with the present invention a photographic element isprovided comprising a support and at least one photo-sensitive silverhalide emulsion layer, wherein said element comprises, dispersed in ahydrophilic water-permeable colloid binder, e.g. gelatin, at least onedye according to the above general formula.

Further in accordance with the present invention a photographic elementis provided comprising a support and at least one photosensitive silverhalide emulsion layer, wherein said element comprises said at least onedye according to the above formula in a solid particle state byacidifying the slightly alkaline coating solution "in situ" at themoment the coating solution is applied.

DETAILED DESCRIPTION OF THE INVENTION

The presence of an amide group as a substituent on the methine chain isvery characteristic for the dyes suitable for use in this invention.

The absence of this amide-group does not only affect the spectralbehavior, shifting the absorption to shorter wavelengths, but doesn'tallow the dye to be decolorized quickly enough, as required in rapidprocessing conditions, especially for 38 s processing cycles.

The synthesis of dyes according to the present invention may followdifferent suitable ways, a schematic way of synthesizing said dye beingillustrated in reaction scheme 1 given hereinafter. ##STR3##

The monomethine dyes can be synthesized via different suitable ways.

One way consists in the conversion of dialkylaminobenzene A to thealpha-keto-ester B. At least three methods are described in literature:

a. The reaction of A with diethyl oxalate in the presence of aluminumtrichloride (Guyot, Compt. Rend. 144, 1120 (1907)).

b. The reaction of A with oxalyl chloride, followed by ethanolysis ofthe intermediate acid chloride (Staudinger, Stockmann, Chem. Ber. 42,224 (1909)).

c. The reaction of A with ethyl oxalyl chloride (Michler, Hanhardt,Chem. Ber. 10,2081(1877)).

The thus obtained ester B is then converted to the amide C by treatmentwith ethanolamine.

Following the second suitable way, amides such as C can be obtaineddirectly by reaction of amines with the intermediate acid chloride as isdescribed (but not for C) in Wright and Gutsell, J. Org. Chem. 24, 265(1959).

Keto-amides such as C can easily be condensed with acidic nuclei such aspyrazolones by several known methods including refluxing the componentsin toluene with azeotropic destillation or refluxing the components inethanol using known catalysts such as amines, amine salts or zincchloride.

Dispersions of the dye obtained following reaction scheme 1 according tothis invention show a maximum absorption peak at a wavelength of 560 nm,said wavelength value being shifted about 100 nm more bathochromicallyin comparison with the corresponding dye without amide-substitution.

Trimethine (and even pentamethine) dyes may be obtained followingreaction scheme 2 according to this invention. ##STR4##

From the prior art it is known that the presence of one or more anionic,weakly-acidic groups in the dyes is important to provide sufficientnon-migratory character at coating pH values in the range of 4 to 8.

In the acid pH range the filter dyes according to the present inventioncan be incorporated in aqueous coating compositions in dispersed form byusing commercial mixing devices for making colloidal dispersions, e.g.in gelatin. The size of the dye particles obtained is chosen tofacilitate coating and rapid decoloration of the dye. Where the dyes areinitially crystallized in the form of particles larger than desired foruse, conventional techniques for achieving smaller particle sizes can beemployed, such as ball milling, roller milling, sand milling and thelike. The solid particle dispersions cannot only be prepared in thepresence of gelatin as a colloidal medium but also e.g. in colloidalsilica. A preferred method of preparing an aqueous solid particledispersion of a photographically useful compound, for incorporation inone of the layers of a photographic silver halide material comprises thesteps of

dissolving a non-watersoluble but alkali-soluble compound in an aqueousalkaline solution, if necessary with the help of an organic watersoluble solvent

precipitating the said compound from said solution in the presence ofcolloidal silica sol, preferably in the further presence of a dispersingagent by lowering the pH of the solution, e.g. by neutralizing with anaqueous acidic solution

removing water-soluble salts formed by the precipitation and any organicsolvent used, and

concentrating the dispersion either during or after the precipitation bydialysis or ultrafiltration or after precipitation by flocculation anddecantation, followed by washing and further decantation.

Said precipitation in the presence of colloidal silica sol preferablyoccurs in the further presence of a dispersing agent, like e.g. a2-N,N,N-trialkylamino-acetic acid and can be performed by simultaneousaddition of an aqueous alkaline solution comprising the alkaline-solublecompound and an aqueous acidic solution, to a stirred solutioncomprising the total or partial amount of colloidal silica sol and ofdispersing agent while keeping the pH constant, preferably at a value ofless than 6.0, the rest of said amount if any being present in at leastone of said solutions.

Preferred dispersing agents used during the preparation of solid silicadispersions are one or more partially ionizable polymer(s) or one ormore surfactant(s) or a combination thereof.

Another possibility to obtain ultra fine dye dispersions consists inacidifying a slightly alkaline coating composition during thepreparation of the coating composition or "in situ" just before coatingit onto the supporting layer. It has been found that the application ofthis dosage technique allows us to obtain the dyes in a very fine solidparticle form, homogeneously divided into the coated layer so that solidparticles can hardly be observed even by means of microscopictechniques.

The non-diffusing dyes the synthesis of which has been describedhereinbefore and which are added to a hydrophilic layer of aphotographic element as a solid particle have a mean diameter of lessthan 10 μm, more preferably less than 1 μm and still more preferablyless than 0.1 μm.

At a pH of at least 10 the dispersed filter dyes are easily solubilizedso they are removed almost completely from a hydrophilic waterpermeablecolloid layer of a photographic silver halide emulsion material by itscommon alkaline aqueous liquid processing and leave almost no residualstain. The presence of sulfite in the processing solution contributes toa more rapid discoloration of the filter dyes.

Particularly for 38 s processing cycles, comprising a development,fixing, rinsing and drying step, photographic elements with dyesaccording to this invention in one or more hydrophilic layers are veryrapidly discolored.

The hydrophilic colloidal layer(s) in which the dye(s) are incorporatedin accordance with the present invention can be a backing layer, anantihalation undercoating layer, a silver halide emulsion layer, anintermediate layer and a protective outermost-layer.

Emulsion layers in accordance with this invention may containlight-sensitive silver halide crystals with a diameter of at least 0.1μm. Intermediate layers in accordance with the present invention maycontain very fine light-insensitive silver halide particles with adiameter of 10 to 100 nm known as Lippmann emulsions, incorporated intosaid layers e.g. to serve as scavengers to prevent oxidized developerproducts to migrate into adjacent layers.

The layers previously mentioned as suitable layers comprising a filteror antihalation dye may be incorporated in e.g. X-ray materials, graphicarts materials, diffusion transfer materials, black and white or colorcinematographic materials etc.

According to a preferred embodiment the dye or dyes are incorporated ina antihalation back coating layer for single-coated materials or aantihalation undercoating layer or layers, especially for double-coatedmaterials as e.g. X-ray photographic materials.

In an outermost layer or layers or in an emulsion layer or layers one ormore dyes according to this invention may be used to adjust thesensitivity of the photographic material as required by the productionspecifications. So it is possible to apply a dosing feeder just beforecoating the hydrophilic layer concerned and to control the production ofthe photographic material in this way, the dye(s) being present in theform of a gelatinous dispersion or in a solid particle state.

The dyes absorbing in the green spectral range being frequently usedtrimethine dyes can be used advantageously between silver halideemulsion layers of double-sided emulsion coated (duplitized)photographic film material applied in X-ray recording for use with greenlight emitting X-ray conversion phosphor screens. By said arrangementthe green light that would cross the support and to some extent becomescattered thereby, is considerably attenuated and cannot give rise to anunsharp image into an opposite silver halide emulsion layer.

Green light emitting phosphor screens and their use in combination withgreen sensitive silver halide emulsion layers of a double side coated(duplitized) film are described e.g. in U.S. Pat. No. 4,130,428, whereinalso several measures, e.g. the use of filter dyes, to reduce cross-overlight have been described.

In a particular embodiment of the present invention the dyes areincorporated into a radiographic material that is provided at both sidesof the support with a silver halide emulsion layer and an antistresslayer as a protective layer coated thereover. The radiographic materialpreferably has on both sides of the film support silver halide emulsioncoatings that are split into two distinctive emulsion layers havingsilver halide crystals of different average grain size one of which is ahigh speed emulsion layer and the other is a low speed emulsion layer;the high speed emulsion layer being situated at a larger distance fromthe support than the low speed emulsion layer. This way thesensitometric curve can be fine-tuned, giving the perfect profile forthe specific application. The layer arrangement may also be opposite tothe previously cited sequence in order to get a higher contrast.Moreover even without using a separate anticrossover layer this layerarrangement reduces crossover, especially in the critical low densityarea. In the presence of crossover preventing antihalation undercoatlayers containing the dyes according to this invention the crossoverreduction is improved without leaving a color stain upon processing,especially upon rapid processing in less than 60 seconds, preferably in38 seconds as a reference processing time of materials withhigh-throughput.

All combinations of symmetrically double-sized films with a symmetric orasymmetric set of intensifying screens or combinations of double-sizedfilms with asymmetric emulsion layers, whether or not duplitized, incombination with a symmetric or asymmetric set of intensifying screenscan be useful, depending on the specific needs required.

According to another embodiment said green-light absorbing dyes can beused in a antihalation layer of a photographic silver halide emulsionmaterial in order to improve image sharpness by absorbing exposure lightpenetrating the emulsion layer(s) into the direction of the support. Theuse of said mainly green light absorbing dyes in an antihalation layeris particularly advantageous in silver halide emulsion materials thatare made spectrally sensitive to green light and of which the exposureproceeds with a green light emitting laser e.g. argon ion laser the mainpower of which is emitted at 488 and 514 nm.

The following examples illustrate the present invention without howeverlimiting it thereto.

EXAMPLES

In Table I, formulae of the dyes as used in the examples are given.

                  TABLE I                                                         ______________________________________                                        Formulae of the dyes used in the examples.                                    ______________________________________                                        Dye 1 (invention)                                                              ##STR5##                      (I)                                            Dye 2 (comparative example 1, corresponding to Dye 1 of Table                 1 of US-P 4,857,446)                                                           ##STR6##                      (II)                                           Dye 3 (comparative example 2, corresponding to Dye 11 of                      Table 2 of US-P 4,857,446)                                                     ##STR7##                      (III)                                          ______________________________________                                    

SYNTHESIS OF THE MONOMETHINE DYE 1

89.4 ml of oxalyl chloride and 500 ml diethylether were placed in areactor vessel and colled to 0° C. A solution of N,N-dimethylaniline in500 ml diethyl ether was carefully added over a period of 1 hr. Thereaction mixture was stirred overnight at 0° C., after which time 183 mlethanolamine was added, followed by a solution of 80 g NaOH in 1000 mlwater. The yellow precipitate (193 g) was filtered and was shown to havean amide structure corresponding to formula B, given hereinbefore. 1.18g of the amide, 1.09 g 1-(4-carboxyphenyl)-3-methyl pyrazolone and 1 gZnCl₂ were refluxed in 25 ml ethanol for 24 hrs. The resulting redprecipitate (1.9 g) was rinsed with acetone and dried, and was shown byspectroscopy to have the structure of product C (dye 1) givenhereinbefore.

OPTICAL PROPERTIES OF THE DYES COATED AS A DISPERSION ON A FILM SUPPORT

Procedure for the preparation of the dye dispersion

10 g of filter dye was dispersed at 40° C. in 200 g of a 10% aqueousgelatin solution by using a rotating pearl mill containing as a millingmaterial zirconium oxide pearls sizing 0.6 to 0.8 μm. At a dye particlesize of about 1 μm the milling process was stopped and the dispersionseparated from the milling material.

Coating procedure

Chromium (III) acetate as a hardening agent and an additional amount ofgelatin were added to the above prepared dye dispersion kept at atemperature of 36° C. and a pH value of 6.1.

Said dispersion was double-side coated and dried on a polyethyleneterephthalate film support of 175 μm thickness in order to obtain ateach side a dye coverage of0.1 g/m², a gelatin coverage of 1 g/m² and acoverage of hardening agent of 0.016 g/m².

In Table II the maximum absorption wavelength (λ-max) of the coatedmaterials is given together with the half band width (HWB) values of theabsorption wavelength expressed in nm, the density (D) measured at λ-maxand at 540 nm, the latter being the main emission wavelength of a Gd₂ O₂S:Tb phosphor used in X-ray intensifying screens. Absorption spectrawere measured at a Diano Corporation

Match Scan spectrophotometer with diffuse light.

                  TABLE II                                                        ______________________________________                                        Optical properties of dyes in the coated layer.                                         λ-max                                                                           HBW                                                        Dye No.   (nm)     (nm)    D at λ-max                                                                      D at 540 nm                               ______________________________________                                        1 (invention)                                                                           560      166     0.41     0.40                                      2 (comparison)                                                                          455      176     0.43     0.24                                      3 (comparison)                                                                          500      231     0.63     0.60                                      ______________________________________                                    

In order to assess the resistance to diffusion of the dye in the coatedlayer, the above described coating of each dye was rinsed with destilledwater at 20° C. for 5 minutes. Before and after rinsing the spectraldensity D at λ-max was measured at the double-side coated material ashas been summarized in Table III.

                  TABLE III                                                       ______________________________________                                        Density measured at the maximum absorption wavelength λ-max.                       D at λ-max                                                 Dye No.       Before rinsing                                                                            After rinsing                                       ______________________________________                                        1 (invention) 0.41        0.40                                                2 (comparison)                                                                              0.43        0.43                                                3 (comparison)                                                                              0.63        0.62                                                ______________________________________                                    

The negligible change in spectral density D at λ-max before and afterrinsing with water is a measure for the resistance to diffusion of thedye in the coating layer.

DECOLORIZING PROPERTIES OF THE DYES, COATED IN AN ANTI-CROSSOVER LAYER,UNDER PRACTICAL PROCESSING CONDITIONS

To check the decolorizing properties of the dyes in practicalcircumstances the dyes were coated on both sides of a polyethyleneterephtalate film support in an anti-cross-over layer and wereovercoated with an emulsion layer and a protective layer. The dyecoverage was adjusted so that the optical density at 540 nm was 0.15 forthe double side coated sample. Next, the samples were processed in a 90or 38 seconds processing cycle and the spectral density at λ-max of thedye was determined. A low value of this spectral density means that thedye decolorizes well during the processing. The composition of thesample coatings, developer and fixers and the processing conditions aregiven hereinafter: Composition of the coated samples.

In the emulsion layer no use was made of a spectral sensitizer becauseof the interference of its absorption spectrum with the dyes underinvestigation. The coating weight, expressed in g/m² per side of thedifferent layers, was as follows:

    ______________________________________                                        anti-cross-over layer:                                                        gelatin                   1 g/m.sup.2                                         dye                       see Table IV                                        chromium(III) acetate     0.016 g/m.sup.2                                     emulsion layer: all amounts are given in g/m.sup.2                            AgBr(I)-crystals (2 mole % of iodide; 98 mole % of                                                      4.15                                                bromide) (as AgNO.sub.3)                                                      gelatin                   2.10                                                4-hydroxy-6-methyl-1,3,3a,7-                                                                            0.006                                               tetraazaindene                                                                sorbitol                  0.20                                                protective layer:                                                             gelatin                   1.10                                                polymethylmethacrylate    0.023                                               (average particle diameter: 6 μm)                                          formaldehyde              0.10                                                ______________________________________                                    

Processing conditions and composition of developers.

Conditions for the 90 seconds processing cycle.

processing machine: CURIX 402 (Agfa-Gevaert trade name) with thefollowing time (in seconds (sec.)) and temperature (in °C.)characteristics:

loading: 3.4 sec.

developing: 23.4 sec./35° C. in developer AGFA G138 (trade name)

cross-over: 3.8 sec.

fixing: 15.7 sec./35° C. in fixer AGFA G334 (trade name)

cross-over: 3.8 sec.

rinsing: 15.7 sec./20° C.

drying: 32.2 sec. (cross-over time included)

total time: 98.0 sec.

Conditions for the 38 seconds processing cycle.

processing machine: CURIX HT530 (Agfa-Gevaert trade name) with thefollowing time (in seconds (sec.)) and temperature (in ° C)characteristics:

loading: 0.2 sec.

developing: 9.3 sec./35° C. in developer II described hereinafter

cross-over: 1.4 sec.

rinsing: 0.9 sec.

cross-over: 1.5 sec.

fixing: 6.6 sec./35° C. in fixer II described hereinafter

cross-over: 2.0 sec.

rinsing: 4.4 sec.

cross-over: 4.6 sec.

drying: 6.7 sec.

total time: 37.6 sec.

Composition of the three-part developer for the 38 seconds processingcycle

    ______________________________________                                        concentrated part A                                                           hydroquinone                 106.0 g                                          potassium sulphite (65% solution)                                                                          249.0 g                                          potassium bromide            12.0 g                                           ethylenediamine tetraacetic acid,                                                                          9.6 g                                            sodium salt trihydrate                                                        potassium hydroxyde          77.0 g                                           potassium carbonate          38.0 g                                           sodiumtetraborate, decahydrate                                                                             70.0 g                                           5-methylbenzotriazole        0.076 g                                          diethylene glycol            56.0 g                                           demineralized water to make 1 liter                                           pH adjusted to 11.80 at 25° C. with potassium hydroxide.               concentrated part B:                                                          phenidone (1-phenyl-3-pyrazolidinone)                                                                      20.0 g                                           acetic acid                  30.1 g                                           5-nitro-indazole             1.15 g                                           diethylene glycol to make 100 ml                                              concentrated part C:                                                          glutaric dialdehyde 50% solution)                                                                          17.8 g                                           potassium metabisulphite     26.0 g                                           water to make 100 ml                                                          ______________________________________                                    

For initiation of the processing the three parts were mixed in thefollowing ratio: 250 ml of part A, 700 ml of water, 25 ml of part B and25 ml of part C. No starter solution was added. A pH of 10.40 at 25° C.was measured.

    ______________________________________                                        Composition of fixer II (containing a hardener)                               concentrated part A:                                                          ammoniumthiosulphate (78% solution)                                                                     661     g                                           sodium sulphite           54      g                                           boric acid                25      g                                           sodium acetate trihydrate 70      g                                           acetic acid               40      g                                           water to make 1 liter                                                         pH adjusted with acetic acid to 5.30 at 25° C.                         concentrated part B:                                                          water                     150     ml                                          acetic acid               10      g                                           sulphuric acid            13      g                                           aluminium sulphate (34% solution)                                                                       27      g                                           water to make 250 ml                                                          ______________________________________                                    

The fixer ready for use was then made by mixing concentrated part A,water and concentrated part B in the following ratio: respectively 250ml, 687.5 ml and 62.5 ml. A pH of this mixture of 4.25 at 25° C wasmeasured.

Densities at λ-max of the dyes after processing are given in Table IV.

                  TABLE IV                                                        ______________________________________                                        Evaluation of the optical densities of the dyes.                                                        optical density at                                             coated dye amount                                                                            λ-max                                        Dye No.    in             after processing                                    cycle      g/m.sup.2 per side                                                                           90 s cycle 38 s                                     ______________________________________                                        1 (invention)                                                                            0.038          0.000      0.020                                    2 (comparison)                                                                           0.063          0.000      0.015                                    3 (comparison)                                                                           0.025          0.005      0.025                                    ______________________________________                                    

As can be seen from Table IV, even in the 38 s-processing cycle theoptical density at the maximum absorption wavelength is reduced to anacceptable level.

EVALUATION OF THE PHOTOGRAPHIC PROPERTIES OF THE DYES IN ANANTI-CROSS-OVER LAYER

Coating procedure

The coatings of item 3 were repeated, except for the addition per moleof AgNO₃ used for the emulsion of 470 mg of the spectral sensitizeranhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbo-cyaninehydroxide. In addition a coating without a dye added to theanti-cross-over layer was performed as a reference.

Exposure, sensitometric and densitometric data:

Samples of those coatings were exposed with green light of 540 nm during0.1 seconds using a continous wedge and were processed during the 90seconds cycle described below. The density as a function of the lightdose was measured and therefrom were determined the followingparameters:

fog level (with an accuracy of 0.001 density),

the relative speed S at a density of 1 above fog (the sample with thecomparative example was adjusted to a relative speed value of 100),

Determination of the cross-over percentage:

The cross-over percentage (% cross-over) was determined as follows. Thedouble side coated samples were adjusted between a single green lightemitting screen (CURIX ortho Regular: Agfa-Gevaert trade name) and awhite paper, replacing the second screen. This film-screen element,directed with its light emitting screen to the X-ray tube, was thenexposed with varying X-ray doses, expressed as log E. After processingthese samples in the 90 seconds cycle, the minimal dose (log E) neededto obtain a density of 0.5 above fog was determined for the frontlayer(log E front) and the backlayer (log E back) separately. The cross-overpercentage was then calculated according to the following equation:

    % cross-over=100/antilog(logE back-logE front)

In table V the results of these photographic tests are tabulated.

                  TABLE V                                                         ______________________________________                                        Photographic effect of the dyes in an anti-cross-over                         layer: sensitometry and cross-over percentage.                                sample      coated dye amount                                                                           sensitometry                                        Dye No.     per side (g/m.sup.2) fog                                                                    speed   % cross-over                                ______________________________________                                        no dye (reference)                                                                        0        0.016    100   40                                        dye 1 (invention)                                                                         0.038    0.017    83    30                                        dye 2 (comparison)                                                                        0.063    0.017    89    31                                        dye 3 (comparison)                                                                        0.025    0.017    83    28                                        ______________________________________                                    

This table shows that the dyes (invention and comparative examples)significantly reduce the cross-over percentage with an acceptabledecrease in sensitivity. It is further shown that fog is not influencedin the presence of the dyes, and that even with a significantly lowercoating weight, the dye according to the invention shows a similarcrossover percentage as dye 2 used in the comparative coating. Besideseven versus dye 3, which is coated in a lower amount and which showssimilar sensitometric results and cross-over characteristics, thedecolorizing properties are better for the dye in accordance with thisinvention, especially for shorter processing cycles, e.g. the 38 scycle, as has been shown in Table IV hereinbefore.

We claim:
 1. A photographic material comprising a support and at leastone light-sensitive silver halide emulsion layer characterized in thatit comprises in a hydrophilic colloid layer at least one filter dyecorresponding to the following general formula (I): ##STR8## wherein nrepresents 0 or 1;p represents 0, 1 or 2; Q represents the atomsnecessary to form an acidic nucleus R₁ represents hydrogen, substitutedor unsubstituted alkyl, substituted or unsubstituted aryl, COOR₂,NHCOR₃or NHSO₂ R₄ with R₂ representing hydrogen or substituted orunsubstituted alkyl, R₃ and R₄ representing substituted or unsubstitutedalkyl, or substituted or unsubstituted aryl, X represents OR₅, SR₅ orNR₆ R₇, wherein R₅ represents H, substituted or unsubstituted alkyl,substituted or unsubstituted aryl and each of R₆ and R₇ which may be thesame or different represents hydrogen, substituted or unsubstitutedalkyl, substituted or unsubstituted aryl or the necessary atoms, to forma ring together with the N-atom to which they are attached and theC-atom of the phenylene ring in ortho position with respect to saidN-atom; R₆ and R₇ together represent the necessary atoms to form a ringwith the N-atom to which they are attached; L₁, L₂, L₃ representsubstituted or unsubstituted methine with the proviso that at least oneof L₁, L₂ or L₃ must be substituted by --CONR₈ R₉ ; R₈ and R₉ which maybe the same or different represent hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted aryl, NH₂, NHR₁₀, NR₁₁R₁₂ with R₁₀, R₁₁ and R₁₂ representing a substituted or unsubstitutedalkyl, or a substituted or unsubstituted aryl and wherein at least oneof R₁ to R₁₂ contains an ionizable group.
 2. A photographic materialaccording to claim 1 wherein said at least one dye is a filter dyecorresponding to the following general formula (II): ##STR9## whereineach of n, p, X, R₁, L₁, L₂ and L₃ has one of the meanings given inclaim 1 and whereinR₁₃ represents hydrogen, substituted or unsubstitutedalkyl, substituted or unsubstituted aryl, or sulfolanyl, R₁₄ representshydrogen, substituted or unsubstituted alkyl, substituted orunsubstituted aryl,COOR₂, NHCOR₃, NHSO₂ R₄, with R₂, R₃ and R₄representing hydrogen, substituted or unsubstituted alkyl, orsubstituted or unsubstituted aryl, and wherein at least one of R₁ to R₁₄contains an alkali-soluble group.
 3. A photographic material accordingto claim 1 wherein said at least one filter dye is incorporated into anantihalation undercoat layer coated between the support and at least onesilver halide emulsion layer.
 4. A photographic material according toclaim 1 wherein said at least one filter dye is incorporated into abacking layer.
 5. A photographic material according to claim 1 whereinthe dye(s) is(are) present in a hydrophilic colloid layer in an amountof 0.01 to 1.0 mmole/m².
 6. A photographic material according to claim 1wherein the filter dye(s) is(are) present as a gelatinous dispersion(s).7. A photographic material according to claims 1 wherein the filterdye(s) is(are) present as solid silica particle dispersion(s).
 8. Aphotographic material according to claim 1 wherein said photographicmaterial is an X-ray material.
 9. Use of a photographic materialaccording to claim 8 for rapid processing applications shorter than 60seconds, comprising imagewise exposure of the material followed by postexposure processing comprising developing, fixing, rinsing and dryingsteps.
 10. A photographic material according to claim 1 wherein in thegeneral formula (I) the said acidic nucleus represents a pyrazolone,barbituric acid, thiobarbituric acid, rhodanine, hydantoine,oxazolidindione, thio-oxazolidindione or isoxazolinone nucleus.